US3709778A - Method for bleaching groundwood pulp with tertiary butyl hydroperoxide - Google Patents
Method for bleaching groundwood pulp with tertiary butyl hydroperoxide Download PDFInfo
- Publication number
- US3709778A US3709778A US00105961A US3709778DA US3709778A US 3709778 A US3709778 A US 3709778A US 00105961 A US00105961 A US 00105961A US 3709778D A US3709778D A US 3709778DA US 3709778 A US3709778 A US 3709778A
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- US
- United States
- Prior art keywords
- bleaching
- pulp
- tertiary butyl
- butyl hydroperoxide
- hydrogen peroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Definitions
- ABSTRACT Bleaching of ligneous cellulosic materials such as groundwood pulp by treating the pulp with an aqueous solution of tertiary butyl hydroperoxide and a buffering agent and thereafter contacting the pulp with a sulfite compound.
- This invention relates to a method for preparing ligneous cellulosic materials of improved brightness, in particular, paper pulp by bleaching with tertiary butyl hydroperoxide, and in a particular embodiment, aftertreating with a sulfite compound.
- Hydrogen peroxide is used advantageously in bleaching high yield pulps such as groundwood, despite its high cost because with careful use it can bleach without causing yield losses or without reducing the degree of polymerization of the cellulose. Hydrogen peroxide is also used as a finishing bleach in kraft paper manufacture after the non-cellulosic components have been reduced by a series of steps including chlorination, alkaline washing and chlorine dioxide bleaching.
- peracetic acid in particular peracetic acid in conjunction with chlorine dioxide have also been proposed as bleaching agents.
- Peracetic acid is extremely unstable and decomposes with explosive violence at about i 10 C. and therefore must be handled with extreme caution at low temperatures.
- paper pulp can be bleached by replacing hydrogen peroxide with an equal amount of the more stable tertiary butyl hydroperoxide.
- the brightness increase obtained either by hydrogen peroxide or by tertiary butyl hydroperoxide has been found to be the same. It will be obvious, therefore, that since tertiary butyl hydroperoxide is available at a much more favorable price than the same weight of hydrogen peroxide, there is a valuable saving in using the hydroperoxide.
- That tertiary butyl hydroperoxide can be utilized as a bleaching agent is completely unexpected in view of the wide differences in chemical reactivity among tertiary butyl hydroperoxide, hydrogen peroxide and the peracids.
- olefins in general, are converted smoothly and in good yields to the corresponding epoxides by peracids at low temperatures (0 25 C.) while similar results are obtained with hydroperoxides only at higher temperatures 1 20 C.) and only in the presence of a transition metal catalyst such as molybdenum.
- Hydrogen peroxide does not epoxidize olefins either in the presence or in the absence of catalysts.
- Ketones are converted to esters and lactones by peracids while much poorer results are obtained with hydrogen peroxide and then only in the presence of a base as a catalyst. Hydroperoxides on the other hand do not react with ketones.
- Base catalyzed hydrogen peroxide converts aromatic aldehydes and ketones having an amino or a hydroxyl group in the ortho or para position to the corresponding amino phenols or polyphenols but neither hydroperoxides nor peracids can be used in this reaction. These differences in chemical reactivity therefore render the use of tertiary butyl hydroperoxide as a bleaching agent to be completely unexpected.
- Tertiary butyl hydroperoxide provides additional advantages over hydrogen peroxide and the peracids.
- lt is stable in aqueous solutions and does not require stabilizing agents. It does not lose its bleaching strength in the presence of metallic ions such as Fe, Co, Ni, etc. ions whereas hydrogen peroxide for example must be stabilized and is most effective only with sequestering agents being present or alternatively by removing the metal ions from the pulp solution prior to bleaching.
- tertiary butyl hydroperoxide provides an exceedingly important advantage over hydrogen peroxide or the peracids such as peracetic acid in that it is an excellent agent for preventing microbiological attack on the pulp.
- This feature is a unique and important advantage since molds or other microbiological growths on pulp follow through the process and finally degrade the quality of the finished paper.
- tertiary butyl hydroperoxide is utilized to bleach ligneous cellulosic materials such as paper pulp.
- the bleaching agent is combined with a mild buffering agent such as sodium carbonate, sodium bicarbonate or the combination of sodium tripolyphosphate and a surfaetant.
- a mild buffering agent such as sodium carbonate, sodium bicarbonate or the combination of sodium tripolyphosphate and a surfaetant.
- hydroperoxide bleaching step is followed by an aftertreatment step with sodium sulfite, sodium bisulfite or the like.
- the process of this invention is particularly adapted for the bleaching of cellulosic fibers and materials that are derived from lignin-containing materials by any of the processes that are generally used for fiber liberation.
- the invention is particularly applicable to the bleaching of groundwood pulp, i.e., pulp containing large amounts of lignin.
- groundwood pulp i.e., pulp containing large amounts of lignin.
- this invention is also applicable to treating any pulps which are treated with hydrogen peroxide at some stage in their manufacture, for example, kraft pulp.
- tertiary butyl hydroperoxide can be produced at a price much lower than that of hydrogen peroxide and since equal weights of hydrogen peroxide and tertiary butyl hydroperoxide give equally good bleaching there is a considerable advantage for utilizing the hydroperoxide.
- organic hydroperoxides have the additional advantage of having greater stability as compared with hydrogen peroxide. Hydrogen peroxide, unless special precautions are followed as has been described, decomposes to give water and oxygen which is not suitable for bleaching. Such precautions are unnecessary with organic hydroperoxides since they decompose only at temperatures above 90 C.
- Sulfite compounds which can be used include Na SO sodium bisulfite or sodium hydrogen sulfite, Nal-ISO or sulfites produced in situ by bubbling sulfur dioxide into the alkaline solution. These are the preferred after-treatment materials.
- a mild buffering agent such as sodium carbonate, sodium bicarbonate or the combination of sodium tripolyphosphate with a surfactant is combined with the tertiary butyl hydroperoxide in the bleaching step.
- Anionic surfactants are particularly preferred, the most preferred materials being the sodium alkylbenzene sulfonates.
- Particularly preferred are the linear alkylbenzene sulfonates wherein the alkyl group contains from about 11 to 14 carbon atoms with an average of about 12 carbon atoms since these materials are biodegradable.
- the tripolyphosphate-surfactant combination gives excellent results, whenever pollution is a problem, the carbonate or bicarbonate can be used equally well. None of these are in any way bleaching agents, but enhance the bleaching ability of the tertiary butyl hydroperoxide to an unexpected extent.
- the amount of tertiary butyl hydroperoxide utilized to treat the pulp is in the same range as that utilized by the industry for hydrogen peroxide treating. In general, amounts ranging between 0.1 weight per cent to 2 weight per cent based on the weight of dry pulp can be used, although larger amounts also can be employed.
- the amount of sulfite, for example, sodium bisulfite for the after-treatment may range between I per cent and 6 per cent although this is not critical and lower or higher amounts may be employed. If S0 is employed an equivalent amount is used.
- Sodium silicate is the recommended buffer for hydrogen peroxide bleaching and it is known that hydrogen peroxide is less effective in the absence of a buffer. It was found, however, that tertiary butyl hydroperoxide requires no strong alkali. This is desirable since the possibility of cellulosic breakdown which can occur under alkaline conditions is completely avoided.
- tertiary butyl hydroperoxide as a bleaching agent was compared directly with hydrogen peroxide.
- Laboratory tests were standardized and based on TAPPI Routine Control test methods.
- the pulp employed was a commercial balsam plus pine groundwood.
- the pulp as received has a photovolt reflectance (brightness) of 65.
- an acceptable color improvement by hydrogen peroxide or similar competitive bleaching agents is l0 units, i.e., a Photovolt value of 75. Since such an improvement is difficult to achieve under the most carefully controlled conditions, improvements in excess of IO units are very unusual and are deemed extremely difficult to obtain.
- the test method consists of first conditioning the pulp.
- the pulp as received contains approximately per cent water.
- a slurry of this pulp in 9 weights of water is allowed to stand overnight, then mixed for 10 minutes with a wire beater and filtered in a Buchner funnel for 15 minutes using a rubber dam.
- the resulting cake is used as stock for the bleaching test.
- the cake in general, contains about 20 to 25 per cent dry pulp.
- a sufficient amount of the stock prepared as described above is mixed with water in a polyethylene bag to give a per cent consistancy, i.e., 10 grams of dry pulp and 90 grams of total water. Under these conditions most of the water is absorbed by the pulp and there is little free liquid.
- the bleaching agent and buffer if any, is added in an aqueous solution (generally about a 1.0 weight per cent solution of the bleaching agent) in an amount such that the desired quantity based on dry pulp of the bleaching agent and buffer is added to the pulp solution in the bag.
- the bag is kneaded to mix the pulp and bleach solution and is then immersed in a water bath at 170 F. for one hour. On removal from the bath the sulfite aftertreat agent is mixed by kneading and after minutes the pulp is poured onto a Buchner funnel where the superficial liquid is removed through a filter paper.
- the pulp on the funnel is covered by a second piece of filter paper and placed between layers of felt.
- the pulp pad covered by the filter paper and felt is squeezed between rubber rollers and then hung in an air current to air dry for 12 to 16 hours with the filter paper covers in place.
- the hand sheet is dried in an oven at 1 10 C. for one hour. Following the oven drying step the amount of bleaching obtained is determined by measuring the reflectance by a Model 610 Photovolt reflectometer and comparing it with a hand sheet made by the same procedure without bleaching or after-treat solution.
- the Photovolt reflectometer for this purpose uses a blue filter and the brightness values thus obtained can be converted to the TAPPI official General Electric Brightness values.
- the Photovolt reflectometer is adjusted so that a standard magnesium oxide block reads 100 per cent reflectance.
- THBP tertiary butyl hydroperoxide
- Amounts of bleaching agent ranging between 0.1 weight per cent and 5 weight per cent based on the dry pulp are satisfactory and amounts of buffering agent, if used, can range between 0.5 and 10.0 per cent.
- EXAMPLE ll Another series of bleaching runs were carried out in a similar manner as that employed in Example l except that sodium carbonate and sodium bicarbonate, respectively, were used as the buffering agents in combination with the tertiary butyl hydroperoxide bleaching agent in amounts ranging between 3.0 and 10.0 per cent by weight based on the weight of the dry pulp. Equally good brightening of the pulp was obtained as in the comparable runs of Example 1.
- pulps bleached with tertiary butyl hydroperoxide upon standing show no tendency to discolor due to microbiological attack whereas pulps bleached with hydrogen peroxide, for example, become discolored because of such attacks by microorganisms.
- a method of bleaching lignin-containing groundwood pulp which comprises contacting said lignin-containing groundwood pulp with an aqueous solution consisting essentially of tertiary butyl hydroperoxide and a buffering agent selected from the group consisting of sodium carbonate, sodium bicarbonate, and the combination of sodium tripolyphosphate with a surfactant and thereafter contacting with a sulfite compound the lignin-containing groundwood pulp which has been contacted with the aqueous tertiary butyl hydroperoxide solution and buffering agent, said sulfite compound being in an amount sufficient to avoid color reversion.
- said surfactant is a linear alkylbenzene sulfonate wherein the alkyl group contains from 1 1 to 14 carbon atoms.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
Abstract
Description
Claims (5)
- 2. The method according to Claim 1, wherein said buffer-ing agent is sodium carbonate.
- 3. The method according to Claim 1, wherein said buffer-ing agent is sodium bicarbonate.
- 4. The method according to Claim 1, wherein said buffer-ing agent is sodium tripolyphosphate and a surfactant.
- 5. The method according to Claim 4, wherein said surfactant is a linear alkylbenzene sulfonate wherein the alkyl group contains from 11 to 14 carbon atoms.
- 6. The method according to claim 1, wherein said sulfite compound is sodium sulfite or sodium bisulfite.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10596171A | 1971-01-12 | 1971-01-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3709778A true US3709778A (en) | 1973-01-09 |
Family
ID=22308734
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US00105961A Expired - Lifetime US3709778A (en) | 1971-01-12 | 1971-01-12 | Method for bleaching groundwood pulp with tertiary butyl hydroperoxide |
Country Status (1)
Country | Link |
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US (1) | US3709778A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5284597A (en) * | 1992-12-23 | 1994-02-08 | S. C. Johnson & Son, Inc. | Aqueous alkaline soft-surface cleaning compositions comprising tertiary alkyl hydroperoxides |
US5447602A (en) * | 1993-08-26 | 1995-09-05 | Henkel Corporation | Process for repulping wet-strength paper |
US6428653B1 (en) | 2000-12-04 | 2002-08-06 | West Fraser Timber Co. Ltd. | Method of bleaching with formamidine sulfinic acid using a reducing agent to eliminate residual peroxide |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1767543A (en) * | 1928-02-15 | 1930-06-24 | Pilot Lab Inc | Process of bleaching cellulose products |
US2860944A (en) * | 1955-11-28 | 1958-11-18 | Du Pont | Bleaching fibers of vegetable origin with formamidine sulfinate and alkaline peroxide |
US3458394A (en) * | 1965-10-08 | 1969-07-29 | Scott Paper Co | Pulping wood chips with peracetic acid and chlorine dioxide |
US3467575A (en) * | 1964-08-13 | 1969-09-16 | Hooker Chemical Corp | Process of bleaching paper with peracetic acid |
-
1971
- 1971-01-12 US US00105961A patent/US3709778A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1767543A (en) * | 1928-02-15 | 1930-06-24 | Pilot Lab Inc | Process of bleaching cellulose products |
US2860944A (en) * | 1955-11-28 | 1958-11-18 | Du Pont | Bleaching fibers of vegetable origin with formamidine sulfinate and alkaline peroxide |
US3467575A (en) * | 1964-08-13 | 1969-09-16 | Hooker Chemical Corp | Process of bleaching paper with peracetic acid |
US3458394A (en) * | 1965-10-08 | 1969-07-29 | Scott Paper Co | Pulping wood chips with peracetic acid and chlorine dioxide |
Non-Patent Citations (1)
Title |
---|
Noller, Chemistry of Organic Compounds, 1951, pgs. 792 793. * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5284597A (en) * | 1992-12-23 | 1994-02-08 | S. C. Johnson & Son, Inc. | Aqueous alkaline soft-surface cleaning compositions comprising tertiary alkyl hydroperoxides |
US5447602A (en) * | 1993-08-26 | 1995-09-05 | Henkel Corporation | Process for repulping wet-strength paper |
US6428653B1 (en) | 2000-12-04 | 2002-08-06 | West Fraser Timber Co. Ltd. | Method of bleaching with formamidine sulfinic acid using a reducing agent to eliminate residual peroxide |
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AS | Assignment |
Owner name: ATLANTIC RICHFIELD COMPANY Free format text: MERGER AND CHANGE OF NAME;ASSIGNORS:ATLANTIC RICHFIELD COMPANY (MERGED INTO);ATLANTIC RICHFIELD DELAWARE CORPORATION (CHANGED TO);REEL/FRAME:004911/0380 Effective date: 19850314 Owner name: ARCO CHEMICAL COMPANY,PENNSYLVANIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ATLANTIC RICHFIELD COMPANY;REEL/FRAME:004911/0448 Effective date: 19870831 Owner name: ARCO CHEMICAL COMPANY, 1500 MARKET STREET, PHILADE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ATLANTIC RICHFIELD COMPANY;REEL/FRAME:004911/0448 Effective date: 19870831 |
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Owner name: ARCO CHEMICAL TECHNOLOGY, INC., A CORP. OF DE, DEL Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ARCO CHEMICAL COMPANY;REEL/FRAME:005010/0113 Effective date: 19880831 |